Aqueous cleaning compositions comprising cationic copolymers

ABSTRACT

The invention relates to aqueous compositions, preferably aqueous compositions comprising at least one polymer with a particle size of more than 10 μm, formed from the polymerisation of a) at least one monomer of formula (I), wherein R 1 , signifies hydrogen or methyl, R 2  signifies hydrogen or C 1 -C 4 alkyl, R 3  signifies C 1 -C 4 alkylene, R 4 , R 5  and R 6  signify independently from each other hydrogen or C 1 -C 4 alkyl, X signifies —O— or —NH— and Y signifies Cl; Br; l; hydrogen-sulphate or methosulfate, b) and/or at least one non-ionic monomer, c) at least one cross-linking agent in an amount of 0-50 ppm by the weight of component a) and b) optionally at least one chain transfer agent with the proviso that (i) if the polymer is a cationic homopolymer then the amount of the crosslinking agent is always more than 0 ppm and less than 50 ppm.

This invention relates to aqueous compositions comprising homo- and/orcopolymers as thickeners, as well as to new acidic aqueous cleaningformulations.

It is standard practice to include viscosifying polymers in acidicaqueous household formulations in order to achieve optimum rheologycharacteristics. Various polymer types have been proposed for thepurpose of increasing the viscosity of household formulations.

EP-A-458599 refers to fabric treatment compositions consisting of anaqueous base, fabric softening materials and a deflocculating polymer.

WO-A-99/06455 describes thickening agents for acidic compositions, whichinclude cationic homopolymers with 50 to 600 ppm cross-linking agents.The preferred range of cross-linking agent is between 60 and 250 ppm.

Although the polymers used in aqueous compositions described in theprior art do achieve viscosification of the composition, there is stilla need to provide further improvement in rheology profile. This isparticularly important where the aqueous composition is expected toperform under a number of different conditions and environments.

The invention relates to aqueous compositions comprising at least onepolymer, with a particle size of more than 10 μm, formed from thepolymerisation of

-   -   a) at least one monomer of formula (I)

-   -   -   wherein        -   R₁ signifies hydrogen or methyl,        -   R₂ signifies hydrogen or C₁-C₄alkyl,        -   R₃ signifies C₁-C₄alkylene,        -   R₄, R₅ and R₆ signify independently from each other hydrogen            or C₁-C₄alkyl,        -   X signifies —O— or —NH— and        -   Y signifies Cl; Br; I; hydrogensulphate or methosulfate,

    -   b) and/or at least one non-ionic monomer,

    -   c) at least one cross-linking agent in an amount of 0-50 ppm by        the weight of component a) and

    -   d) optionally at least one chain transfer agent with the proviso        that        -   (i) if the polymer is a cationic homopolymer then the amount            of the crosslinking agent is always more than 0 ppm and less            than 50 ppm.

The used polymer can be added to the aqueous composition in solid orliquid form. The solid form can be further classified into

-   (i) powder, or-   (ii) beads, which are non-dusting particles.

If the polymer is added to the composition in solid form, the beads formis preferred.

Preferably, the aqueous composition has a pH-value <7. More preferably,the pH-value is <5.

Preferably, the aqueous compositions are acidic household formulations.More preferably the aqueous formulations are acidic general-purposecleaners for hard surfaces.

The polymer is added to the composition while in the form of particles,which have a volume average size of more than 10 μm and up to 1000 μm,preferably more than 50 μm, especially preferred from 100 μm and up to1000 μm. The size of the particles can be determined by known methods,i.e. with laser diffraction.

In a preferred embodiment of the Invention, the polymer is a cationichomopolymer, wherein the amount of the crosslinking agent is always morethan 0 ppm and less than 50 ppm.

In a further preferred embodiment of the invention, the polymer is anon-ionic homopolymer.

In a further preferred embodiment of the invention, the component a)comprises 10-100% by weight (wt-%) of at least one cationic monomer and0-90 wt-% of at least one non-ionic monomer.

In a more preferred embodiment of the invention, the component a)comprises 30-100 wt-% of at least one cationic monomer and 0-70 wt-% ofat least one non-ionic monomer. In an even more preferred embodiment ofthe invention, the component a) comprises 40-100 wt-% of at least onecationic monomer and 0-60 wt-% of at least one nonionic monomer.

In an especially preferred embodiment of the invention, the component a)comprises 50-95 wt-% of at least one cationic monomer and 5-50 wt-% ofat least one non-ionic monomer. The weight percentages relate to thetotal weight of the polymer

Preferred cationic monomers are compounds of formula (I)

-   wherein-   R₁ signifies hydrogen or methyl,-   R₂ signifies hydrogen or C₁-C₄alkyl,-   R₃ signifies C₁-C₄alkylene,-   R₄, R₅ and R₆ signify independently from each other hydrogen or    C₁-C₄alkyl,-   X signifies —O— or —NH— and-   Y signifies Cl; Br; I; hydrogensulphate or methosulfate.

The alkyl groups may be linear or branched. The alkyl groups are methyl,ethyl, propyl, butyl and isopropyl.

Preferred non-ionic monomers are N-vinyl pyrrolidone or compounds offormula (II)

-   wherein-   R₇ signifies hydrogen or methyl,-   R₈ signifies hydrogen or C₁-C₄alkyl, and-   R₉ and R₁₀ signify independently from each other hydrogen or    C₁-C₄alkyl.

Preferably, the cross-inking agent b) contains at least twoethylenically unsaturated moieties. Suitable preferred cross-liningagents are divinyl benzene; tetra allyl ammonium chloride; allyacrylates and methacrylates; diacrylates and dimethacrylates of glycolsand polyglycols; butadiene; 1,7-octadiene; allyl-acrylamides andally-methacrylamides; bisacrylamidoacetic acid;N,N′-methylene-bisacrylamide and polyol polyallylethers, such aspolyallylsaccharose and pentaerythrol triallylether.

More preferred cross-linking agents are tetra ally ammonium chloride;allyl-acrylamides and allyl-methacrylamides; bisacrylamidoacetic acidand N,N′-methylene-bisacrylamide.

The most preferred cross-linking agents are tetra ally ammonium chlorideand N,N′-methylene-bisacrylamide.

It is also suitable to use mixtures of cross-linking agents.

The cationic homopolymer is always crosslinked by at least onecross-linking agent b). Preferably, the crosslinker(s) is (are) presentin the range of from 0.5-49 ppm (based on the component a).

Preferably, the chain transfer agent c) is selected from mercaptanes,malic acid, lactic acid, formic acid, isopropanol and hypophosphites.

In a preferred embodiment of the invention the chain transfer agent c)is present in a range of from 0 to 1000 ppm, more preferably 0-500 ppm,most preferably 0-300 ppm (based on the component a).

It is also suitable to use mixtures of chain transfer agents.

In a preferred embodiment of the present invention the aqueouscomposition comprises 0.005 to 15 wt-% of the polymer with a particlesize of more than 10 μm, more preferably 0.01 to 10 wt-%, mostpreferably 0.01 to 5 wt-%. The weight percentages relate to the totalamount of the aqueous formulation.

In a preferred embodiment of the present invention, the aqueouscomposition, preferably the acidic aqueous composition, comprises atleast one copolymer and/or homopolymer with a particle size of more than10 μm, preferably more than 50 μm, more preferably from 100 μm and up to1000 μm, formed from the polymerisation of

-   -   a) at least one monomer of formula (Ia)

-   -   -   wherein        -   R₁ signifies hydrogen or methyl,        -   R₂ signifies hydrogen or methyl,        -   R₃ signifies C₁-C₂alkylene and        -   Y signifies Cl; Br or I, and

    -   b) at least one cross-linking agent selected from divinyl        benzene; tetra allyl ammonium chloride; ally acrylates and        methacrylates; diacrylates and dimethacrylates of glycols and        polyglycols; butadiene; 1,7-octadiene; allyl-acrylamides and        ally-methacrylamides; bisacrylamidoacetic acid;        N,N′-methylene-bisacrylamide and polyol polyallylethers in an        amount of 0-50 ppm (based on the component a), and

    -   c) optionally at least one chain transfer agent selected from        mercaptanes; malic acid; lactic acid; formic acid; isopropanol        and hypophosphites in an amount of 0-1000 ppm, preferably 0-500        ppm, more preferably 0-300 ppm (based on the component a),        with the proviso that

    -   (i) if the polymer is a homopolymer then the amount of the        crosslinking agent(s) is always more than 0 ppm and less than 50        ppm.

In a further preferred embodiment of the present invention, the aqueouscomposition, preferably the acidic aqueous composition, comprises atleast one copolymer and/or homopolymer with a particle size of more than10 μm, preferably more than 50 μm, more preferably from 100 μm and up to1000 μm, formed from the polymerisation of

-   -   a) at least one monomer of formula (IIa)

-   -   -   wherein        -   R₇ signifies hydrogen or methyl, and        -   R₈ signifies hydrogen; methyl or ethyl,

    -   b) at least one cross-linking agent selected from divinyl        benzene; tetra allyl ammonium chloride; allyl acrylates and        methacrylates; diacrylates and dimethacrylates of glycols and        polyglycols; butadiene; 1,7-octadiene; allyl-acrylamides and        allyl-methacrylamides; bisacrylamidoacetic acid;        N,N′-methylene-bisacrylamide and polyol polyallylethers in an        amount of 0-50 ppm (based on the component a), and

    -   c) optionally at least one chain transfer agent selected from        mercaptanes; malic acid; lactic acid; formic acid; Isopropanol        and hypophosphites in an amount of 0-1000 ppm, preferably 0-500        ppm, more preferably 0-300 ppm (based on the component a),.

In a more preferred embodiment of the present invention, the aqueouscomposition, preferably the acidic aqueous composition, comprises atleast one copolymer with a particle size of more than 10 μm, preferablymore than 50 μm, more preferably from 100 μm and up to 1000 μm, formedfrom the polymerisation of

-   -   a) at least one monomer of formula (Ia)

-   -   -   wherein        -   R₁ signifies hydrogen or methyl,        -   R₂ signifies hydrogen or methyl,        -   R₃ signifies C₁-C₂alkylene and        -   Y signifies Cl; Br or I, and

    -   b) at least one monomer of formula (IIa)

-   -   -   wherein        -   R₇ signifies is hydrogen or methyl, and        -   R₈ signifies hydrogen; methyl or ethyl,

    -   c) at least one cross-linking agent selected from divinyl        benzene; tetra allyl ammonium chloride; allyl acrylates and        methacrylates; diacrylates and dimethacrylates of glycols and        polyglycols; butadiene; 1,7-octadiene; allyl-acrylamides and        allyl-methacrylamides; bisacrylamidoacetic acid;        N,N′-methylenebisacrylamide and polyol polyallylethers in an        amount of 0-50 ppm (based on the component a), and

    -   d) optionally at least one chain transfer agent selected from        mercaptanes; malic acid; lactic acid; formic acid; isopropanol        and hypophosphites in an amount of 0-1000 ppm, preferably 0-500        ppm, more preferably 0-300 ppm (based on the component a).

In an especially preferred embodiment of the present invention, theaqueous composition, preferably the acidic aqueous composition,comprises 0.005-15% by weight, preferably 0.01-10 wt-%, more preferably0.01-5 wt-% based on the total weight of the composition of at least onecopolymer with a particle size of more than 10 μm, preferably more than50 μm, more preferably from 100 μm and up to 1000 μm, formed from thepolymerisation of

-   -   a) at least one monomer of formula (Ia)

-   -   -   wherein        -   R₁ signifies hydrogen or methyl,        -   R₂ signifies hydrogen or methyl,        -   R₃ signifies C₁-C₂alkylene and        -   Y signifies Cl; Br or I, and

    -   b) at least one monomer of formula (IIa)

-   -   -   wherein        -   R₇ signifies hydrogen or methyl, and        -   R₈ signifies hydrogen; methyl or ethyl,

    -   c) at least one cross-linking agent selected from divinyl        benzene; tetra ally ammonium chloride; allyl acrylates and        methacrylates; diacrylates and dimethacrylates of glycols and        polyglycols; butadiene; 1,7-octadiene; allyl-acrylamides and        allyl-methacrylamides; bisacrylamidoacetic acid;        N,N′-methylene-bisacrylamide and polyol polyallylethers in an        amount of 0-50 ppm (based on the component a), and

    -   d) optionally at least one chain transfer agent selected from        mercaptanes; malic acid; lactic acid; formic acid; isopropanol        and hypophosphites in an amount of 0-1000 ppm, preferably 0-500        ppm, more preferably 0-300 ppm (based on the component a).

In an important embodiment of the present invention, the aqueouscomposition, preferably the acidic aqueous composition, comprises0.005-15% by weight, preferably 0.01-10 wt-%, more preferably 0.01-5wt-% based on the total weight of the composition, of at least onecopolymer with a particle size of more than 10 μm, preferably more than50 μm, more preferably from 100 μm and up to 1000 μm, formed from thepolymerisation of

-   -   a) 40-95 wt-%, preferably 50-95 wt-%, based on the total weight        of the copolymer, of at least one monomer of formula (Ia)

-   -   -   wherein        -   R₁ signifies hydrogen or methyl,        -   R₂ signifies hydrogen or methyl,        -   R₃ signifies C₁-C₂alkylene and        -   Y signifies Cl; Br or I, and

    -   b) 5-60 wt-%, preferably 5-50 wt-%, based on the total weight of        the copolymer, of at least one monomer of formula (IIa)

-   -   -   wherein        -   R₇ signifies hydrogen or methyl, and        -   R₈ signifies hydrogen; methyl or ethyl,

    -   c) at least one cross-linking agent selected from divinyl        benzene; tetra allyl ammonium chloride; allyl acrylates and        methacrylates; diacrylates and dimethacrylates of glycols and        polyglycols; butadiene; 1,7-octadiene; allyl-acrylamides and        allyl-methacrylamides; bisacrylamidoacetic acid;        N,N′-methylene-bisacrylamide and polyol polyallylethers in an        amount of 0-50 ppm (based on the component a), and

    -   d) optionally at least one chain transfer agent selected from        mercaptanes; malic acid; lactic acid; formic acid; isopropanol        and hypophosphites in an amount of 0-1000 ppm, preferably 0-500        ppm, more preferably 0-300 ppm (based on the component a).

The aqueous compositions are useful as acidic household compositions.Acidic household compositions can be any common known formulations, suchas general-purpose cleaners for cleaning hard surfaces, acid householdcleaners (bath) or WC cleaners.

The aqueous formulation can be used on many different surface types,such as ceramic, fiber glass, polyurethane and plastic surfaces.

A preferred embodiment of the present invention relates to acidicaqueous compositions, which are transparent.

Household cleaning agents are aqueous or alcoholic (for example ethanolor isopropyl alcohol) solutions of one or more of the followingcomponents:

-   -   anionic, nonionic, amphoteric and/or cationic surfactants,    -   soaps, prepared by saponification of animal and vegetable        greases, like coconut and tallow grease,    -   organic acids, like hydrochloric acid, phosphoric acid, citric        acid, acetic acid or sulfuric acid,    -   for basic products inorganic (NaOH or KOH) or organic bases like        triethanolamine,    -   abrasives for improved cleaning of surfaces, such as silicas,        seed kernel, polyethylene or calciumcarbonate,    -   waxes and/or silicones for maintenance and protection of        surfaces,    -   polyphosphates,    -   substances, which eliminate hypochlorite or halogens;    -   peroxides comprising bleaching activators like TAED, for example        sodium perborate, H₂O₂ or hypochlorite;    -   enzymes;    -   cleaning agents based on wax may comprise solvents selected from        benzine, turpentine and/or paraffines and emulsifiers based on        wax;    -   filling agents like silicates, polyphosphates, such as sodium or        potassium tripolyphosphate, Zeolithes for powdery cleaning        agents;    -   pigments, lakes or soluble dyes;    -   perfumes; and    -   light stabilizers, antioxidants, antimicrobials, UV-absorbers        and chelating agents.

The actual active ingredient and the actual minimum effective amountwill be determined by the actual product/application in which thethickened composition is to be used.

A further embodiment of the present invention is a hard surface cleaningcomposition comprising:

-   (i) 0.005-15 wt-%, preferably 0.01-10 wt-%, more preferably 0.01-5    wt-% of at least one polymer as defined above, based on the total    weight of the composition,-   (ii) 1-80 wt-% based on the total weight of the composition, of at    least one detergent and/or at least one soap and/or at least one    salt of a saturated C₈-C₂₂ fatty acid and/or at least one    unsaturated C₈-C₂₂ fatty acid,-   (iii) 0-50 wt-% based on the total weight of the composition, of at    least one alcohol,-   (iv) 0-50 wt-% based on the total weight of the composition, of    typical ingredients for cleaning composition,-   (v) 0-50 wt-% based on the total weight of the composition, of at    least one acid, and-   (vi) tap water or deionised water ad 100 wt-%.

The pH-value of the aqueous acidic compositions is <7, preferably <5.

A more preferred hard surface cleaner composition comprises

-   (i) 0.005-15 wt-%, preferably 0.01-10 wt-%, more preferably 0.01-5    wt-% based on the total weight of the composition, of at least one    homopolymer and/or copolymer with a particle size of more than 10    μm, preferably more than 50 μm, more preferably from 100 μm and up    to 1000 μm, formed from the polymerisation of    -   a) at least one monomer of formula (Ia)

-   -   -   wherein        -   R₁ signifies hydrogen or methyl,        -   R₂ signifies hydrogen or methyl,        -   R₃ signifies C₁-C₂alkylene and        -   Y signifies Cl; Br or I,

    -   b) at least one cross-linking agent selected from divinyl        benzene; tetra allyl ammonium chloride; allyl acrylates and        methacrylates; diacrylates and dimethacrylates of glycols and        polyglycols; butadiene; 1,7-octadiene; allyl-acrylamides and        allyl-methacrylamides; bisacrylamidoacetic acid;        N,N′-methylene-bisacrylamide and polyol polyallylethers in an        amount of 0-50 ppm (based on the component a), with the proviso        that        -   (i) if the polymer is a homopolymer then the amount of the            crosslinking agent(s) is always more than 0 ppm and less            than 50 ppm, and

    -   c) optionally at least one chain transfer agent selected from        mercaptanes; malic acid; lactic acid; formic acid; isopropanol        and hypophosphites in an amount of 0-1000 ppm, preferably 0-500        ppm, more preferably 0-300 ppm (based on the component a),

-   (ii) 1-80 wt-% based on the total weight of the composition, of at    least one detergent and/or at least one soap and/or at least one    salt of a saturated C₈-C₂₂ fatty acid and/or at least one    unsaturated C₈-C₂₂ fatty acid,

-   (iii) 0-50 wt-% based on the total weight of the composition, of at    least one alcohol,

-   (iv) 0-50 wt-% based on the total weight of the composition, of    typical ingredients for cleaning composition,

-   (v) 0-50 wt-% based on the total weight of the composition, of at    least one acid, and

-   (vi) tap water or deionised water ad 100 wt-%.

A further preferred hard surface cleaner composition comprises

-   (i) 0.005-15 wt-%, preferably 0.01-10 wt-%, more preferably 0.01-5    wt-% based on the total weight of the composition, of at least one    homopolymer and/or copolymer with a particle size of more than 10    μm, preferably more than 50 μm, more preferably from 100 μm and up    to 1000 μm, formed from the polymerisation of    -   a) of at least one monomer of formula (IIa)

-   -   -   wherein        -   R₇ signifies hydrogen or methyl, and        -   R₈ signifies hydrogen; methyl or ethyl,

    -   b) at least one cross-linking agent selected from divinyl        benzene; tetra allyl ammonium chloride; allyl acrylates and        methacrylates; diacrylates and dimethacrylates of glycols and        polyglycols; butadiene; 1,7-octadiene; allyl-acrylamides and        allyl-methacrylamides; bisacrylamidoacetic acid;        N,N′-methylene-bisacrylamide and polyol polyallylethers in an        amount of 0-50 ppm (based on the component a), and

    -   c) optionally at least one chain transfer agent selected from        mercaptanes; malic acid; lactic acid; formic acid; isopropanol        and hypophosphites in an amount of 0-1000 ppm, preferably 0-500        ppm, more preferably 0-300 ppm (based on the component a),

-   (ii) 1-80 wt-% based on the total weight of the composition, of at    least one detergent and/or at least one soap and/or at least one    salt of a saturated C₈-C₂₂ fatty acid and/or at least one    unsaturated C₈-C₂₂ fatty acid,

-   (iii) 0-50 wt-% based on the total weight of the composition, of at    least one alcohol,

-   (iv) 0-50 wt-% based on the total weight of the composition, of    typical ingredients for cleaning composition,

-   (v) 0-50 wt-% based on the total weight of the composition, of at    least one acid, and

-   (vi) tap water or deionised water ad 100 wt-%.

A more preferred hard surface cleaner composition comprises

-   (i) 0.005-15 wt-%, preferably 0.01-10 wt-%, more preferably 0.01-5    wt-% based on the total weight of the composition, of at least one    copolymer with a particle size of more than 10 μm, preferably more    than 50 μm, more preferably from 100 μm and up to 1000 μm, formed    from the polymerisation of    -   a) 50-95 wt-%, based on the total weight of the copolymer, at        least one monomer of formula (Ia)

-   -   -   wherein        -   R₁ signifies hydrogen or methyl,        -   R₂ signifies hydrogen or methyl,        -   R₃ signifies C₁-C₂alkylene and        -   Y signifies Cl; Br or I, and

    -   b) 5-50 wt-%, based on the total weight of the copolymer, at        least one monomer of formula (IIa)

-   -   -   wherein        -   R₇ signifies hydrogen or methyl, and        -   R₈ signifies hydrogen; methyl or ethyl,

    -   c) at least one cross-linking agent selected from divinyl        benzene; tetra allyl ammonium chloride; allyl acrylates and        methacrylates; diacrylates and dimethacrylates of glycols and        polyglycols; butadiene; 1,7-octadiene; allyl-acrylamides and        allyl-methacrylamides; bisacrylamidoacetic acid;        N,N′-methylene-bisacrylamide and polyol polyallylethers in an        amount of 0-50 ppm (based on the component a), and

    -   d) optionally at least one chain transfer agent selected from        mercaptanes; malic acid; lactic acid; formic acid; isopropanol        and hypophosphites in an amount of 0-1000 ppm, preferably 0-500        ppm, more preferably 0-300 ppm (based on the component a),

-   (ii) 1-80 wt-% based on the total weight of the composition, of at    least one detergent and/or at least one soap and/or at least one    salt of a saturated C₈-C₂₂ fatty acid and/or at least one    unsaturated C₈-C₂₂ fatty acid,

-   (iii) 0-50 wt-% based on the total weight of the composition, of at    least one alcohol,

-   (iv) 0-50 wt-% based on the total weight of the composition, of    typical ingredients for cleaning composition,

-   (v) 0-50 wt-% based on the total weight of the composition, of at    least one acid, and

-   (vi) tap water or deionised water ad 100 wt-%.

As component (ii), anionic, nonionic, or zwitterionic and amphotericsynthetic detergents are suitable.

Suitable anionic detergents are

-   -   sulfates, for example fatty alcohol sulfates, the alkyl chain of        which has from 8 to 18 carbon atoms, for example sulfated lauryl        alcohol;    -   fatty alcohol ether sulfates, for example the acid esters or        salts thereof of a polyaddition product of from 2 to 30 mol of        ethylene oxide and 1 mol of a C₈-C₂₂ fatty alcohol;    -   the alkali metal, ammonium or amine salts, referred to as soaps,        of C₈-C₂₂ fatty acids, for example coconut fatty acid;    -   alkylamide sulfates;    -   alkylamine sulfates, for example monoethanolamine lauryl        sulfate;    -   alkylamide ether sulfates;    -   alkylaryl polyether sulfates;    -   monoglyceride sulfates;    -   alkanesulfonates, the alkyl chain of which contains from 8 to 20        carbon atoms, for example dodecyl sulfonate;    -   alkylamide sulfonates;    -   alkylaryl sulfonates;    -   α-olefin sulfonates;    -   sulfosuccinic acid derivatives, for example alkyl        sulfosuccinates, alkyl ether sulfosuccinates or        alkylsulfosuccinamide derivatives;        -   N-[alkylamidoalkyl]amino acids of formula

-   -   -   wherein            -   X is hydrogen, C₁-C₄alkyl or —COO-M+,            -   Y is hydrogen or C₁-C₄alkyl,            -   Z is

-   -   -   -   m₁ is from 1 to 5,            -   n is an Integer from 6 to 18 and            -   M is an alkali metal cation or amine cation,

    -   alkyl and alkylaryl ether carboxylates of formula CH₃—X—Y-A        wherein        -   x is a radical of formula —(CH₂)₅₋₁₉—O—,

-   -   R is hydrogen or C₁-C₄alkyl,    -   Y is —(CHCHO)₁₋₅₀—,    -   A is (CH₂)_(m2-1)—COO-M⁺,    -   m₂ is from 1 to 6 and    -   M is an alkali metal cation or amine cation.

Also used as anionic surfactants are fatty acid methyl taurides, alkylisothionates, fatty acid polypeptide condensation products and fattyalcohol phosphoric acid esters. The alkyl radicals occurring in thosecompounds preferably have from 8 to 24 carbon atoms.

The anionic surfactants are generally in the form of their water-solublesalts, such as the alkali metal, ammonium or amine salts. Examples ofsuch salts include lithium, sodium, potassium, ammonium, triethylamine,ethanolamine, diethanolamine and triethanolamine salts. The sodium,potassium or ammonium (NR₄R₅R₆) salts, especially, are used, with R₄, R₅and R₆ each independently of the others being hydrogen, C₁-C₄alkyl orC₁-C₄hydroxyalkyl.

Especially preferred anionic surfactants in the composition according tothe invention are monoethanolamine lauryl sulfate or the alkali metalsalts of fatty alcohol sulfates, especially sodium lauryl sulfate andthe reaction product of from 2 to 4 mol of ethylene oxide and sodiumlauryl ether sulfate.

Zwitterionic detergents contain both basic and acidic groups which forman inner salt giving the molecule both cationic and anionic hydrophilicgroups over a broad range of pH values. Some common examples of thesedetergents are described in U.S. Pat. Nos. 2,082,275, 2,702,279 and2,255,082, incorporated herein by reference. Suitable zwitterionicdetergent compounds have the formula

wherein

-   R₇ is an alkyl radical containing from about 8 to about 22 carbon    atoms,-   R₈ and R₉ are independently from each other alkyl radical containing    from 1 to about 3 carbon atoms,-   R₁₀ is an alkylene chain containing from 1 to about 3 carbon atoms,-   X is selected from the group consisting of hydrogen and a hydroxyl    radical,-   Y is selected from the group consisting of carboxyl and sulfonyl    radicals and wherein the sum of the R₇, R₈ and R₉ radicals is from    about 14 to about 24 carbon atoms. Amphoteric and ampholytic    detergents which can be either cationic or anionic depending upon    the pH of the system are represented by detergents such as    dodecyl-beta-alanine, N-alkyltaurines such as the one prepared by    reacting dodecylamine with sodium isothionate according to the    teaching of U.S. Pat. No. 2,658,072, N-higher alkylaspartic acids    such as those produced according to the teaching of U.S. Pat. No.    2,438,091, and the products sold under the trade name “Miranol,” and    described in U.S. Pat. No. 2,528,378, said patents being    Incorporated herein by reference.

Further suitable zwitterionic and amphoteric surfactants includeC₈-C₁₈betaines, C₈-C₁₈sulfobetaines,C₈-C₂₄alkylamido-C₁-C₄alkylenebetaines, imidazoline carboxylates,alkylamphocarboxycarboxylic acids, alkylamphocarboxylic acids (e.g.lauroamphoglycinate) and N-alkyl-β-aminopropionates or-iminodipropionates, with preference being given toC₁₀-C₂₀alkylamido-C₁-C₄akylenebetaines and especially to coconut fattyacid amide propylbetaine.

Nonionic surfactants that may be mentioned include, for example,derivatives of the adducts of propylene oxide/ethylene oxide having amolecular weight of from 1000 to 15 000, fatty alcohol ethoxylates (1-50EO), alkylphenol polyglycol ethers (1-50 EO), polyglucosides,ethoxylated hydrocarbons, fatty acid glycol partial esters, for examplediethylene glycol monostearate, fatty acid alkanolamides anddialkanolamides, fatty acid alkanolamide ethoxylates and fatty amineoxides. Nonionic synthetic detergents comprise a class of compoundswhich may be broadly defined as compounds produced by the condensationof alkylene oxide groups (hydrophilic in nature) with an organichydrophobic compound, which may be aliphatic or alkyl aromatic innature. The length of the hydrophilic or polyoxyalkylene radical whichis condensed with any particular hydrophobic group can be readilyadjusted to yield a water-soluble compound having the desired degree ofbalance between hydrophilic and hydrophobic elements

As component (ii) there may also be used the salts of saturated andunsaturated C₈-C₂₂ fatty acids (soap) either alone or in the form of amixture with one another or in the form of a mixture with otherdetergents mentioned as component (ii). Examples of such fatty acidsinclude, for example, capric, lauric, myristic, palmitic, stearic,arachidic, behenic, caproleic, dodecenoic, tetradecenoic, octadecenoic,oleic, eicosenoic and erucic acid, and the commercial mixtures of suchacids, such as, for example, coconut fatty acid. Such acids are presentin the form of salts, there coming into consideration as cations alkalimetal cations, such as sodium and potassium cations, metal atoms, suchas zinc and aluminium atoms, and nitrogen-containing organic compoundsof sufficient alkalinity, such as amines and ethoxylated amines. Suchsalts may also be prepared in situ.

The fatty acids used in making the soaps can be obtained from naturalsources such as, for instance, plant or animal-derived glycerides (e.g.,palm oil, coconut oil, babassu oil, soybean oil, castor oil, tallow,whale oil, fish oil, tallow, grease, lard and mixtures thereof). Thefatty acids can also be synthetically prepared (e.g., by oxidation ofpetroleum stocks or by the Fischer-Tropsch process).

Alkali metal soaps can be made by direct saponification of the fats andoils or by the neutralization of the free fatty acids which are preparedin a separate manufacturing process. Particularly useful are the sodiumand potassium salts of the mixtures of fatty acids derived from coconutoil and tallow, i.e., sodium and potassium tallow and coconut soaps.

The term “tallow” is used herein in connection with fatty acid mixtureswhich typically have an approximate carbon chain length distribution of2.5% C₁₄, 29% C₁₆, 23% C₁₈, 2% palmitoleic, 41.5% oleic and 3% linoleic(the first three fatty acids listed are saturated). Other mixtures withsimilar distribution, such as the fatty acids derived from variousanimal tallows and lard, are also included within the term tallow. Thetallow can also be hardened (i.e., hydrogenated) to convert part or allof the unsaturated fatty acid moieties to saturated fatty acid moieties.When the term “coconut oil” is used herein ft refers to fatty acidmixtures which typically have an approximate carbon chain lengthdistribution of about 8% C₈, 7% C₁₀, 48% C₁₂, 17% C₁₄, 9% C₁₆, 2% C₁₈,7% oleic, and 2% linoleic (the first six fatty acids listed beingsaturated). Other sources having similar carbon chain lengthdistribution such as palm kernel oil and babassu oil are included withthe term coconut oil.

As component (iii) there come into consideration as dihydric alcoholsespecially those compounds having from 2 to 6 carbon atoms in thealkylene moiety, such as ethylene glycol, 1,2- or 1,3-propanediol, 1,3-,1,4- or 2,3-butanediol, 1,5-pentanediol and 1,6-hexanediol.

Preference is given to 1,2-propanediol (propylene glycol).

Preferred monohydric alcohols are ethanol, n-propanol and isopropanoland mixtures of those alcohols.

As component (iv) the thickened aqueous compositions may furthercomprise conventional ingredients known to be used therein. Suchingredients may be perfumes; colorants; bactericide; enzymes such asprotease; dyes; chelants; further viscosity modifiers, such as xanthangum; pigments; solvents; corrosion inhibitors; preservatives;antioxidants: hydrotropes; and builder such as carboxylic acid detergentincluding citric and tartaric acids.

Exemplary acids uses as component (v) compositions of the presentinvention include, without limitation, citric, sulfuric, hydrochloric,phosphoric, acetic, hydroxyacetic, and sulfamic acids.

The polymers used in the acidic aqueous compositions are obtainable byconventional polymerisation processes.

A preferred polymerisation process is the commonly known inversesuspension technique in a hydrocarbon solvent in the presence of apolymeric stabilizer. The polymerisation process being initiated by aredox coupler. A dry polymer is recovered by azeotropic distillation ofwater and solvent

A) Synthesis of the Cationic Polymer

This example illustrates the preparation of a suitable cationic polymer.

An ‘aqueous phase’ of water soluble components is prepared by admixingtogether the following components:

51 g of acrylamid, 118 g of methyl chloride quaternised dimethylaminoethyl acrylate 0.13 g of a sequesterant 0.0044 g of potassium bromate0.06125 g of 2,2-azobis(2-amidinopropane)dihydrochloride and water.

A continuous ‘oil phase’ Is prepared by admixing together the followingcomponents:

300 g of Exxsol ® D40 (dearomatised hydrocarbon solvent) 2 g a polymericstabilizer

The continuous phase was deoxygenated by nitrogen gas for 20 minutes.Afterwards, the phase was agitated with a Rushton turbine stirrer at 400rpm.

The monomer solution was then added to the agitated continuous phase andallowed to disperse for 3 minutes. The temperature of the suspension wasadjusted to 25° C. The suspension was initiated by addition of Sulphurdioxide in Solvent D40 (0.656 ml of a 1% vol/vol solution).

When the exothermic reaction was completed, water was azeotroped off thesuspension under reduced pressure. The resulting suspension of polymerbeads was cooled to 25° C., filtered and air-dried. The obtainedparticle size of the polymer beads is about 240 μm. The size is measuredwith a Sympatec HELOS laser diffraction apparatus (from Sympatec GmbH,Germany).

EXAMPLES 2-15

In analogy to the synthesis of Example 1 the following polymers aresynthesized.

-   Monomer 1 (M1)=dimethylaminoethylacrylate-   Monomer 2 (M2)=acrylamide-   Crosslinker 1 (CL1)=N,N′-methylenebisacrylamide-   Chain Transfer Agent 1 (CTA1)=hypophosphite

Exp. M1 in % M2 in % CL1 in ppm CTA 1 in ppm 2 80 20 0 0 3 80 20 2.5 0 480 20 5 0 5 80 20 8 10 6 80 20 8 5 7 60 40 0 0 8 40 60 0 0 9 60 40 0.5 010 80 20 0.5 0 11 80 20 0.5 15 12 80 20 0.5 25 13 80 20 0.5 35 14 80 2020 35 15 80 20 40 35

The copolymers of Example 2-15 have a particle size of about 240 μm. Thesize is measured with a Sympatec HELOS laser diffraction apparatus (fromSympatec GmbH, Germany).

B) Formulation of a Toilet Cleaner Agent

A composition containing

80 wt-% deion. Water 2.5 wt-% Dobanol ® 25-7 (alcohol ethoxylate) 2.5wt-% Dobanol ® 23-6.5 (alcohol ethoxylate) 15 wt-% citric acidis prepared by adding successively both alcohol ethoxylate and thecitric acid to water under stirring.

The clear and colourless liquid has pH value of 1.7.

C) Formulation of a Bathroom Cleaner Agent

A composition containing

80 wt-% deion. Water 2 wt-% Dehydol ® 04 (Octyl alcohol ethoxytate 4EO)8 wt-% Glucopon ® 215CSUP (Fatty alcohol C₈₋₁₀ polyglycoside) 5 wt-%citric acid 5 wt-% acetic acidis prepared by mixing all components together under stirring.

The clear and colourless liquid has pH value of 2.5.

Addition of the Thickener

The cationic polymer (of A) is slowly added to the both formulations atroom temperature and under stirring until the formulations arehomogenized. All formulations are transparent. The Brookfield viscosityis measured one day after preparation.

Polymer LV Brookfield concentration Viscosity (22° C./ AcidicFormulation Polymer (wt-%) 30 rpm/mPa · s) Toilet Cleaner (B) — 5 ToiletCleaner (B) Polymer of 1.0 1064 Example 1 Toilet Cleaner (B) Polymer of1.0 2000 Example 2 Toilet Cleaner (B) Polymer of 1.0 951 Example 6Toilet Cleaner (B) Polymer of 1.0 1164 Example 8 Bathroom Cleaner (C) —5 Bathroom Cleaner (C) Polymer of 1.0 700 Example 1 Bathroom Cleaner (C)Polymer of 1.0 644 Example 2 Bathroom Cleaner (C) Polymer of 1.0 480Example 6 Bathroom Cleaner (C) Polymer of 1.0 738 Example 7 BathroomCleaner (C) Polymer of 1.0 816 Example 8 Bathroom Cleaner (C) Polymer of1.0 1112 Example 13

1. A hard surface cleaning composition comprising: (i) 0.005-15 wt-%,based on the total weight of the composition, of at least onenon-dusting polymer bead, which polymer bead in a solid form has aparticle size of from 100 μm up to 1000 μm, comprising the polymerformed from the polymerisation of a) at least one monomer of formula (I)

wherein R₁ signifies hydrogen or methyl, R₂ signifies hydrogen orC₁-C₄alkyl, R₃ signifies C₁-C₄alkylene, R₄, R₅ and R₆ signifyindependently from each other hydrogen or C₁-C₄alkyl, X signifies —O— or—NH— and Y signifies Cl; Br; I; hydrogensulphate or methosulfate, b) andat least one non-ionic monomer, wherein the non-ionic monomer is acompound of formula (II)

wherein R₇ signifies hydrogen or methyl, R₈ signifies hydrogen orC₁-C₄alkyl, and R₉ and R₁₀ signify independently from each otherhydrogen or C₁-C₄alkyl, c) at least one cross-linking agent in an amountof 0.5-50 ppm by the weight of component a) and d) optionally at leastone chain transfer agent, which polymer comprises 50-95 wt-% of at leastone cationic monomer of component a) and 5-50 wt-% of at least onenon-ionic monomer component b), (ii) 1-80 wt-% based on the total weightof the composition, of at least one detergent and/or at least one soapand/or at least one salt of a saturated C₈-C₂₂ fatty acid and/or atleast one salt of unsaturated C₈-C₂₂ fatty acid, (iii) 0-50 wt-% basedon the total weight of the composition, of at least one alcohol, (iv)0-50 wt-% based on the total weight of the composition, of typicalingredients for a cleaning composition, (v) 0-50 wt-% based on the totalweight of the composition, of at least one acid, and (vi) tap water ordeionised water ad 100 wt-%, wherein said composition is aqueous andtransparent with a pH of less than
 7. 2. A composition according toclaim 1, wherein components b) and c) are present and the cross-linkingagent of component c) is selected from the group consisting of divinylbenzene; tetra allyl ammonium chloride; allyl acrylates andmethacrylates; diacrylates and dimethacrylates of glycols andpolyglycols; butadiene; 1,7-octadiene; allyl-acrylamides andallyl-methacrylamides; bisacrylamidoacetic acid;N,N′-methylene-bisacrylamide and polyol polyallylethers.
 3. Acomposition according to claim 2, wherein the cross-linking agent ofcomponent c) is selected from the group consisting of tetra allylammonium chloride; ally-acrylamides and allyl-methacrylamides;bisacrylamidoacetic acid and N,N′-methylene-bisacrylamide.
 4. Acomposition according to claim 1, wherein the chain transfer agentcomponent d) is selected from the group consisting of mercaptans; malicacid, lactic acid; formic acid; isopropanol and hypophosphites.
 5. Acomposition according to claim 1, wherein the chain transfer agentcomponent d) is present in a range of from 0 to 1000 ppm based on thecomponent a).
 6. A method of cleaning a hard surface, which comprisescontacting said surface with an effective cleaning amount of a hardsurface cleaning composition according to claim 1 to effect cleaning ofthe surface.